US4745150A - Rubber composition for tire treads - Google Patents

Rubber composition for tire treads Download PDF

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Publication number
US4745150A
US4745150A US06/941,325 US94132586A US4745150A US 4745150 A US4745150 A US 4745150A US 94132586 A US94132586 A US 94132586A US 4745150 A US4745150 A US 4745150A
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US
United States
Prior art keywords
tan
styrene
copolymer
rubber
butadiene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US06/941,325
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English (en)
Inventor
Eiji Ida
Riichiro Ohara
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Toyo Tire Corp
Original Assignee
Toyo Tire and Rubber Co Ltd
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Filing date
Publication date
Application filed by Toyo Tire and Rubber Co Ltd filed Critical Toyo Tire and Rubber Co Ltd
Assigned to TOYO TIRE & RUBBER COMPANY LIMITED, A CORP. OF JAPAN reassignment TOYO TIRE & RUBBER COMPANY LIMITED, A CORP. OF JAPAN ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: IDA, EIJI, OHARA, RIICHIRO
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Publication of US4745150A publication Critical patent/US4745150A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C08L9/08—Latex
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

  • the present invention relates to a rubber composition suitable for tire treads.
  • An object of the invention is to provide a rubber composition for tire treads which has improved traction and enhanced high-speed durability in good balance.
  • Tg glass transition temperature
  • a is the peak value of tan ⁇ determined from a temperature-tan ⁇ dispersion curve.
  • the rubber component of the composition contains at least 30 parts, preferably 50 to 100 parts, of the above-specified solution-polymerized styrene-butadiene copolymer (SBR). If the amount of the copolymer is smaller, the composition fails to afford a tread which is outstanding in various characteristics. Dynamic behavior (traction) and high-speed durability are in conflict with each other. Although various blends of at least two rubbers and different kinds of carbons have heretofore been used in varying quantities to meet these two requirements, satisfactory results still remain to be achieved.
  • SBR solution-polymerized styrene-butadiene copolymer
  • chlorinated butyl rubber (Cl-IIR) which is higher than -60° C. in Tg and at least 40° C. in the above-mentioned mesial width
  • this rubber is inferior in covulcanizability with diene polymers, such that the tread, when incorporating a large amount of the rubber, exhibits poor adhesion to the belt skim rubber and causes separation from the belt skim rubber during running. The rubber therefore leads immediate tire failure and is difficult to use.
  • the solution-polymerized SBR having the foregoing characteristics and to be used in the invention is, for example, an elastic block copolymer prepared by solution polymerization with use of a lithium-base catalyst and comprising one unit of butadiene rubber (BR) block and one unit of random-copolymerized SBR block, the BR block having a vinyl content of 40 to 90%, the SBR block having a vinyl content of 50 to 90% and a styrene content of 30 to 70%, the block copolymer having in its entirety a vinyl content of 50 to 80% and a styrene content of 5 to 30%, at least 40% of the copolymer being coupled with a tin compound so that the coupled copolymer has a BR terminal, the coupled copolymer being higher than -60° C.
  • BR butadiene rubber
  • the peak mesial width of tan ⁇ determined from the temperature range between the two points of intersection of the curve of tan ⁇ -temperature with lines of half of peak of tan ⁇ .
  • SBR prepared by other process and having other micro structure.
  • the lithium-base catalyst is, for example, butyllithium.
  • the BR block has a vinyl content of 40 to 90%
  • the SBR block has a vinyl content of 50 to 90% and a styrene content of 30 to 70%
  • the copolymer has a vinyl content of 50 to 80% and a styrene content of 5 to 30% in its entirety. If these contents are less than the lower limits, poor traction will result, whereas contents exceeding the upper limits entail impaired high-speed durability.
  • the copolymer is coupled with a tin compound so that the copolymer as coupled has a BR block at the terminal.
  • tin compounds are halides, such as fluorides, chlorides, bromides and iodides, of Sn(II) and Sn(IV).
  • the coupling efficiency is at least 40%, preferably 40 to 100%, more preferably 45 to 95%, most preferably 50 to 70%. When the efficiency is at least 40%, improved high-speed durability is available without impairing the dynamic behavior.
  • the coupling efficiency was determined using gel permeation chromatography (GPC), product of Waters, and 0.5 g/100 ml solution of the copolymer in tetrahydrofuran to prepare a molecular weight distribution graph, in which two peaks appeared, one for the coupled high-molecular-weight portion and the other for the unreacted low-molecular-weight portion.
  • the efficiency was calculated from the ratio of the area of the former peak to the entire area.
  • the Tg of the coupled copolymer was measured according to ASTM D3418 using a differential scanning calorimeter (DSC), product of Rigaku Denki Co., Ltd. The above Tg is required to be higher than -60° C. When the TG is lower than -60° C., impaired dynamic behavior (traction) will result although satisfactory high-speed durability is available.
  • At least one of natural rubber (NR) and synthetic rubbers may be used as an ingredient of the rubber component other than the specified SBR.
  • useful synthetic rubbers are polyisoprene rubber (IR), polybutadiene rubber (BR), conventional styrene-butadiene rubber (SBR), modified products of these rubbers, blends of such rubbers, etc.
  • the present invention it is desirable to use 60 to 150 parts, preferably 70 to 120 parts, of carbon black per 100 parts of the rubber component.
  • the rubber composition of the present invention is prepared by mixing the foregoing components together by usual means such as rolls, Banbury mixer or kneader. It is of course possible to incorporate into the composition other known additives such as sulfur, vulcanization accelerator, activator, retarder, carbon black, filler, antioxidant, tackifier, etc.
  • the loss factor tan ⁇ was measured at a rate of rise of temperature of 2° C./min and a frequency of 100 Hz using a spectrometer, product of Iwamoto Seisakusho Co., Ltd.
  • the tires were tested for skid resistance (wet ⁇ ) and drum high-speed endurance according to the methods of Uniform Tire Quality Grading (UTQG), 575,104, one of the consumers' information regulation of the U.S.
  • the tires were also tested for dry ⁇ on an asphalt pavement by substantially the same method as the wet ⁇ test method of UTQG.
  • the high-speed endurance is carried out on wheel tester and the result is expressed in terms of the tire speed when a failure occurred and the time taken for the occurrence of the failure at the speed measured.
  • FIG. 1 is a graph showing how to determine the peak mesial width of tan ⁇ .
  • the rubber composition of Comparative Example 5 listed in Table 1 is a control which was prepared from SBR 1502 (Product of Japan Synthetic Rubber Co., Ltd.) which is a kind of emulsion-polymerized SBR (E-SBR).
  • the carbon black (a) is 118 in the specific surface area (N 2 SA) determined by the nitrogen adsorption method, 120 in iodine adsorption number (IA), 113 in the specific surface area (CTAB) determined by the cetyltrimethylammonium bromide adsorption method, 99 in dibutyl phthalate oil absorption number (24M 4 .DBP) and 115 in tint strength.
  • a to C are solution-polymerized styrene-butadiene block copolymer
  • D to E are random S-SBR
  • F is Cl-IIR
  • G is SBR 1502 (E-SBR).
  • Table 1 reveals that the compositions of Examples 1 and 2 are superior to the control in respect of any of wet ⁇ , dry ⁇ and high-speed durability.
  • the composition of Comparative Example 1 is low in the styrene content of SBR block, is as low as -70° C. in the Tg of the copolymer and is therefore lower in wet ⁇ and dry ⁇ than the control.
  • Comparative Example 2 is great in the styrene content of the copolymer and small in tan ⁇ peak mesial width, so that the composition has yet to be improved in wet ⁇ and dry ⁇ .
  • Comparative Example 3 is great in the styrene content of the copolymer, small in tan ⁇ peak mesial width and considerably high in Tg, consequently permitting great heat generation and resulting in low durability.
  • Comparative Example 4 in which Cl-IIR is used, is poor in adhesion, permits separation in the shoulder portion at early stage and is therefore low in durability.
  • Rubber compositions were prepared in the same manner as in Example 1 with the exception of using the rubber components listed in Table 2. The tires prepared using the compositions were similarly tested for characteristics.
  • Table 2 shows that the composition of Comparative Example 6 in which less than 30 wt.% of polymer A is present still remains to be improved in wet ⁇ and dry ⁇ and is also low in durability.
US06/941,325 1985-12-17 1986-12-15 Rubber composition for tire treads Expired - Fee Related US4745150A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP60-284960 1985-12-17
JP60284960A JPS62143948A (ja) 1985-12-17 1985-12-17 タイヤトレツド用ゴム組成物

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JP (1) JPS62143948A (ja)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0430617A2 (en) * 1989-11-28 1991-06-05 Sumitomo Rubber Industries Limited Radial tyre for passenger cars
EP0443762A2 (en) * 1990-02-17 1991-08-28 Sumitomo Rubber Industries Limited Radial tyre
EP0500338A1 (en) * 1991-02-21 1992-08-26 Sumitomo Rubber Industries Limited Radial tyre for cars equipped with anti-lock braking system
US5227424A (en) * 1988-11-14 1993-07-13 The Yokohama Rubber Co., Ltd. Rubber composition for use as a tire tread
US5290830A (en) * 1991-11-06 1994-03-01 The Goodyear Tire And Rubber Company Reticulated bacterial cellulose reinforcement for elastomers
US5385969A (en) * 1989-11-28 1995-01-31 Sumitomo Rubber Industries, Ltd. Radial tire for passenger cars
US5409988A (en) * 1992-06-08 1995-04-25 Sumitomo Rubber Industries, Ltd. Rubber composition
EP0659821A1 (en) * 1993-12-27 1995-06-28 Sumitomo Rubber Industries Limited Tread rubber composition for tyres
US6063853A (en) * 1996-04-02 2000-05-16 Huels Aktiengesellschaft Tire treads having low rolling resistance and improved ABS braking
US20020091184A1 (en) * 2000-11-20 2002-07-11 Keiji Ikeda Rubber composition for tire and tire using the same
US20070062624A1 (en) * 2000-10-30 2007-03-22 Pirelli Pneumatici Spa Method for improving the grip of a tyre on a snowy and/or icy road, and a winter tyre
CN103797061A (zh) * 2011-09-19 2014-05-14 米其林集团总公司 越野轮胎胎面
CN115702202A (zh) * 2020-06-04 2023-02-14 米其林集团总公司 橡胶配混物

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3812174B1 (en) * 2019-03-01 2023-11-01 Sumitomo Rubber Industries, Ltd. Tire rubber composition and pneumatic tire

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4071496A (en) * 1976-04-30 1978-01-31 Phillips Petroleum Company Carbon black for low-hysteresis rubber compositions
US4111867A (en) * 1976-04-05 1978-09-05 Nippon Zeon Co., Ltd. Rubber composition for tire treads
DE3220680A1 (de) * 1981-06-03 1983-01-05 Bridgestone Tire Co. Ltd. Kautschukmasse fuer kraftfahrzeugreifen
US4383085A (en) * 1980-09-20 1983-05-10 Bridgestone Tire Co., Ltd. Rubber composition for tire
US4398582A (en) * 1980-05-23 1983-08-16 Bridgestone Tire Company Limited Pneumatic tire
JPS58225141A (ja) * 1982-06-25 1983-12-27 Japan Synthetic Rubber Co Ltd ゴム組成物
US4433094A (en) * 1981-08-27 1984-02-21 Bridgestone Tire Company Limited Pneumatic tires comprising an improved thread

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57109817A (en) * 1980-12-26 1982-07-08 Japan Synthetic Rubber Co Ltd Styrene-butadiene block copolymer
JPS60192739A (ja) * 1984-03-15 1985-10-01 Japan Synthetic Rubber Co Ltd ブロック共重合体
DE3561735D1 (en) * 1984-04-18 1988-04-07 Huels Chemische Werke Ag Rubber mixture

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4111867A (en) * 1976-04-05 1978-09-05 Nippon Zeon Co., Ltd. Rubber composition for tire treads
US4071496A (en) * 1976-04-30 1978-01-31 Phillips Petroleum Company Carbon black for low-hysteresis rubber compositions
US4398582A (en) * 1980-05-23 1983-08-16 Bridgestone Tire Company Limited Pneumatic tire
US4383085A (en) * 1980-09-20 1983-05-10 Bridgestone Tire Co., Ltd. Rubber composition for tire
DE3220680A1 (de) * 1981-06-03 1983-01-05 Bridgestone Tire Co. Ltd. Kautschukmasse fuer kraftfahrzeugreifen
US4433094A (en) * 1981-08-27 1984-02-21 Bridgestone Tire Company Limited Pneumatic tires comprising an improved thread
JPS58225141A (ja) * 1982-06-25 1983-12-27 Japan Synthetic Rubber Co Ltd ゴム組成物

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5227424A (en) * 1988-11-14 1993-07-13 The Yokohama Rubber Co., Ltd. Rubber composition for use as a tire tread
AU633655B2 (en) * 1989-11-28 1993-02-04 Sumitomo Rubber Industries, Ltd. Radial tire for passenger cars
EP0430617A3 (en) * 1989-11-28 1991-08-07 Sumitomo Rubber Industries Limited Radial tyre for passenger cars
EP0430617A2 (en) * 1989-11-28 1991-06-05 Sumitomo Rubber Industries Limited Radial tyre for passenger cars
US5385969A (en) * 1989-11-28 1995-01-31 Sumitomo Rubber Industries, Ltd. Radial tire for passenger cars
US5405899A (en) * 1990-02-17 1995-04-11 Sumitomo Rubber Industries, Ltd. Radial tire
AU633179B2 (en) * 1990-02-17 1993-01-21 Sumitomo Rubber Industries, Ltd. Radial tyre
EP0443762A3 (en) * 1990-02-17 1992-02-05 Sumitomo Rubber Industries Limited Radial tyre
EP0443762A2 (en) * 1990-02-17 1991-08-28 Sumitomo Rubber Industries Limited Radial tyre
EP0500338A1 (en) * 1991-02-21 1992-08-26 Sumitomo Rubber Industries Limited Radial tyre for cars equipped with anti-lock braking system
US5290830A (en) * 1991-11-06 1994-03-01 The Goodyear Tire And Rubber Company Reticulated bacterial cellulose reinforcement for elastomers
US5409988A (en) * 1992-06-08 1995-04-25 Sumitomo Rubber Industries, Ltd. Rubber composition
EP0659821A1 (en) * 1993-12-27 1995-06-28 Sumitomo Rubber Industries Limited Tread rubber composition for tyres
US6063853A (en) * 1996-04-02 2000-05-16 Huels Aktiengesellschaft Tire treads having low rolling resistance and improved ABS braking
US20070062624A1 (en) * 2000-10-30 2007-03-22 Pirelli Pneumatici Spa Method for improving the grip of a tyre on a snowy and/or icy road, and a winter tyre
US20020091184A1 (en) * 2000-11-20 2002-07-11 Keiji Ikeda Rubber composition for tire and tire using the same
US6699921B2 (en) * 2000-11-20 2004-03-02 Sumitomo Rubber Industries, Ltd. Rubber composition for tire and tire using the same
CN103797061A (zh) * 2011-09-19 2014-05-14 米其林集团总公司 越野轮胎胎面
US20140221526A1 (en) * 2011-09-19 2014-08-07 Michelin Recherche Et Technique S.A. Off-road tire tread
CN115702202A (zh) * 2020-06-04 2023-02-14 米其林集团总公司 橡胶配混物
CN115702202B (zh) * 2020-06-04 2024-03-19 米其林集团总公司 橡胶配混物

Also Published As

Publication number Publication date
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